The invention relates to a gas discharge lamp fitted with a gas discharge vessel filled with a gas suitable for supporting a gas discharge emitting VUV radiation, with a luminophore coating containing a down conversion luminophore and with means for igniting and maintaining a gas discharge.
Conventional fluorescent lamps are mercury gas discharge lamps, the light emission of which is based on mercury low pressure gas discharge. A mercury low pressure gas discharge emits radiation mainly in the near UV with a maximum at 254 nm which is converted into visible light by UV luminophores.
The mercury gas discharge lamp has a refined technology and with regard to the lamp efficiency xcex7lamp can only be matched or exceeded with difficulty by other lamp technologies.
The mercury in the gas filling is however increasingly regarded as an environmentally harmful and toxic substance which should be avoided as far as possible in modem mass production because of environmental risks in use, production and disposal. Therefore for some time efforts have been concentrated on the development of alternative lamp technologies.
One of the mercury-free or low-mercury alternatives to the conventional mercury gas discharge lamp is the xenon low pressure gas discharge lamp which has a gas filling containing mostly xenon. A gas discharge in a xenon low pressure gas discharge lamp emits vacuum ultraviolet radiation (VUV radiation) in contrast to the UV radiation of the mercury discharge. The VUV radiation is generated by excimers e.g. Xe2*, and is a molecular band radiation with a broad spectrum in the range about 172 nm. Using this lamp technology discharge efficiencies xcex7dis of 65% are achieved.
Another advantage of the xenon low pressure gas discharge lamp is the short response time of the gas discharge which makes it useful as a signal lamp for automobiles, as a lamp for copier or fax devices and as a water disinfection lamp.
However although the xenon low pressure gas discharge lamp has achieved a discharge efficiency xcex7dis which is comparable to that of the mercury gas discharge lamp, the lamp efficiency xcex7lamp of the xenon low pressure gas discharge lamp is still clearly lower than that of the mercury gas discharge lamp.
In principle the lamp efficiency xcex7lamp consists of the components discharge efficiency xcex7dis, luminophore efficiency xcex7phos, the proportion of the generated visible light which leaves the lamp xcex7esc and the proportion xcex7vuv of UV radiation generated by the luminophore:
xcex7lamp=xcex7disxc2x7xcex7phosxc2x7xcex7escxc2x7xcex7vuv. 
One handicap of the conventional xenon low pressure gas discharge lamp lies in the conversion, ineffective in principle, of an energy-rich VUV photon with wavelength of around 172 nm into a comparatively low energy photon from the visible spectrum of 400 nm to 700 nm through the luminophore coating of the lamp. Even if the quantum efficiency of the luminophore is close to 100%, by conversion of a VUV photon into a visible photon, on average 65% of the energy is lost due to radiationless transition.
Surprisingly however it has already been possible to develop VUV luminophores which achieve a quantum efficiency of more than 100% for conversion of VUV photons into visible photons. This quantum efficiency is achieved in that a VUV quantum with an electron energy of 7.3 eV is converted into two visible quantums with an electron energy of 2.5 eV. Such luminophores for xenon low pressure gas discharge lamps are known for example from Renxc3xa9 T. Wegh, Harry Donker, Koentraad D. Oskam, Andries Meijerink xe2x80x9cVisible Quantum Cutting in LiGdF4:Eu3+ through Downconversionxe2x80x9d Science 283, 663.
In analogy to the multiphoton luminophores known for some time, which through xe2x80x9cup conversionxe2x80x9d generate from two visible long-wave photons one short-wave photon, these new luminophores, which generate from one short-wave photon two long-wave photons, are known as down conversion luminophores.
But although the quantum efficiency of the known down conversion luminophores is high, this does not mean that consequently the luminophore efficiency xcex7phos is high. The luminophore efficiency xcex7phos is influenced not only by the quantum efficiency but also by the capacity of the luminophore to absorb the VUV radiation to be converted. The absorption capacity of the known down conversion luminophores is however quite low. Too much energy is lost through undesirable absorption in the lattice and hence the occupation of the excited states reduced.
It is an object of the present invention to develop a gas discharge lamp fitted with a gas discharge vessel filled with a gas suitable for gas discharge which emits VUV radiation, with a luminophore coating which contains a down conversion luminophore and with means for igniting and maintaining a gas discharge, and with improved efficiency.
According to the invention this object is achieved by a gas discharge lamp fitted with a gas discharge vessel filled with a gas filling suitable for supporting a gas discharge emitting VUV radiation, with a luminophore coating containing a down conversion luminophore and with means for igniting and maintaining a gas discharge, in which the down conversion luminophore contains a pair of activators of a first lanthanoid ion and a second lanthanoid ion and a sensitizer selected from the group of the copper (I) ion, silver (I) ion, gold (I) ion, zinc (II) ion, gallium (III) ion, indium (III) ion, thallium (III) ion, germanium (IV) ion, tin (IV) ion and lead (IV) ion.
Particularly advantageous effects in relation to the state of the art are obtained by the invention if the pair of activators of a first lanthanoid ion and a second lanthanoid ion is selected from the group of gadolinium (III)-europium (III); gadolinium (III)-holmium (III); erbium (III)-gadolinium (III) and praseodymium (III)-manganese (II).
As part of the present invention it is preferred that the down conversion luminophore contains a co-sensitizer selected from the group of thallium (I) ion, lead (II) ion, bismuth (III) ion, indium (I) ion, tin (II) ion, antimony (III) ion, gallium (I) ion, germanium (II) ion and arsenic (III) ion.
As part of the present invention it is also preferred for the down conversion luminophore to contain a co-sensitizer selected from the group of the cerium (III) ion, praseodymium (III) ion, neodymium (III) ion, samarium (III) ion, europium (III) ion, gadolinium (III) ion, terbium (III) ion, dysprosium (III) ion, holmium (III) ion, erbium (III) ion, thulium (III) ion, ytterbium (III) ion and lutetium (III) ion.
It can also be preferred for the down conversion luminophore to contain as the first lanthanoid ion the gadolinium (III) ion and as the second lanthanoid ion the holmium (III) ion or the europium (III) ion and a co-activator selected from the group of the terbium (III) ion, ytterbium (III) ion, dysprosium (III) ion, europium (III) ion, samarium (III) ion and manganese (II) ion.
It can also be preferred that the host lattice of the down conversion luminophore is a fluoride.
It is particularly preferred that the down conversion luminophore contains the first lanthanoid ion in a concentration of 10.0 to 99.98 mol %, the second lanthanoid ion in a concentration of 0.01 to 30.0 mol % and the sensitizer in a concentration of 0.01 to 30 mol %.
According to one embodiment of the gas discharge lamp according to the invention the down conversion luminophore contains the sensitizer in a concentration of 5.0 mol % to 20.0 mol %.
In another embodiment of the invention the down conversion luminophore contains the co-sensitizer in a concentration of 0.01 to 30 mol %.
According to a further embodiment of the invention the down conversion luminophore contains the co-activator in a concentration of 0.5 mol %.
The invention also relates to a down conversion luminophore which contains in a host lattice a pair of activators from a first lanthanoid ion and a second lanthanoid ion and a sensitizer selected from the group of the copper (I) ion, silver (I) ion, gold (I) ion, zinc (II) ion, gallium (III) ion, indium (III) ion, thallium (III) ion, germanium (IV) ion, tin (IV) ion and lead (IV) ion.
The luminophore is characterized by a high quantum efficiency, a high absorption of VUV photons and also a high chemical resistance and is therefore particularly suited for commercial applications including in plasma screens. Such a luminophore can advantageously also be used for signaling lamps in motor vehicles.
The invention is now described in more detail.
A gas discharge lamp according to the invention comprises a gas discharge vessel with a gas filling and with at least one wall which has a surface partially transparent to visible radiation with a luminophore layer. The luminophore coating contains a luminophore preparation with an inorganic crystalline host lattice which has obtained its luminosity from activation through an activator pair of a first and a second lanthanoid ion.
The down conversion luminophore is sensitized by a sensitizer from the group of copper (I) ion, silver (I) ion, gold (I) ion, zinc (II) ion, gallium (III) ion, indium (III) ion, thallium (III) ion, germanium (IV) ion, tin (IV) ion and lead (IV) ion. Also the gas discharge lamp is fitted with an electrode structure to ignite the gas discharge and with further means to ignite and maintain the gas discharge.
Preferably the gas discharge lamp is a xenon low pressure gas discharge lamp. Various types of xenon low pressure gas discharge lamps are known which differ in the ignition of the gas discharge. The spectrum of gas discharge first contains a high proportion of VUV radiation invisible to human eye which is converted into visible light in the coating of VUV luminophores on the inside of the gas discharge vessel and then radiated.
The term xe2x80x9cvacuum ultraviolet radiationxe2x80x9d below also refers to electromagnetic radiation with a maximum emission in a wavelength range between 145 and 185 nm.
In a typical construction for the gas discharge lamp this consists of a cylindrical glass lamp bulb filled with xenon, on the wall of which on the outside is arranged a pair of strip-like electrodes electrically isolated from each other. The strip-like electrodes extend over the entire length of the lamp bulb, where their long sides lie opposite each other leaving two gaps. The electrodes are connected to the poles of a high voltage source operated with an alternating voltage of the order of 20 kHz to 500 kHz such that an electric discharge forms only in the area of the inner surface of the lamp bulb.
When an alternating voltage is applied to the electrodes, in the xenon-containing filler gas a silent electrical discharge can be ignited. As a result in the xenon are formed excimers i.e. molecules which consist of an excited xenon atom and a xenon atom in the basic state.
Xe+X*=Xe2* 
The excitation energy is emitted again as VUV radiation with a wavelength of xcex170 to 190 nm. This conversion from electron energy into UV radiation is highly efficient. The generated VUV photons are absorbed by the luminophores of the luminophore layer and the excitation energy partly emitted again in the longer wavelength range of the spectrum.
In principle for the discharge vessel a multiplicity of forms are possible such as plates, single tubes, coaxial tubes, straight, U-shaped, circular curved or coiled, cylindrical or other shape discharge tubes.
As a material for the discharge vessel quartz or glass types are used.
The electrodes consist of a metal e.g. aluminum or silver, a metal alloy or a transparent conductive inorganic compound e.g. ITO. They can be formed as a coating, as an adhesive foil, a wire or a wire mesh.
The discharge vessel is filled with a gas mixture containing a noble gas such as xenon, krypton, neon or helium. Gas fillings which mainly consist of oxygen-free xenon at low gas pressure, e.g. 2 Torr, are preferred. The gas filling can also contain a small quantity of mercury in order to maintain a low gas pressure during discharge.
The inner wall of the gas discharge vessel is coated partly or fully with a luminophore coating which contains one or more luminophores or luminophore preparations. The luminophore layer can also contain organic or inorganic binding agents or a binding agent combination.
The luminophore coating is preferably applied to the inner wall of the gas discharge vessel as a substrate and can comprise a single luminophore layer or several luminophore layers, in particular double layers of a base and a cover layer.
A luminophore coating with base and cover layer allows the quantity of down conversion luminophore in the cover layer to be reduced and in the base layer a less costly luminophore to be used. The base layer preferably contains as a luminophore a calcium-halophosphate luminophore selected to achieve the desired shade of the lamp.
The cover layer contains the down conversion luminophore which thus forms an essential part of the UV radiation generated by gas discharge to be converted directly into the required radiation in the visible range.
An essential feature of the down conversion luminophore according to the invention is that it contains a pair of activators of a first and a second lanthanoid ion and a sensitizer in a host lattice.
The activator pair is preferably selected from the group of gadolinium (III)-europium (III); gadolinium (III)-holmium (III); erbium (III)-gadolinium (III) and praseodymium (III)-manganese (II).
The sensitizer is selected from the group of the copper (I) ion, silver (I) ion, gold (I) ion, zinc (II) ion, gallium (III) ion, indium (III) ion, thallium (III) ion, germanium (IV) ion, tin (IV) ion and lead (IV) ion. Generally these ions are also known according to their electron configuration as d10 ions.
The down conversion luminophore can also contain a co-sensitizer. This can be selected from the group of the thallium (I) ion, lead (II) ion, bismuth (II) ion, indium (I) ion, tin (II) ion, antimony (III) ion, gallium (I) ion, germanium (II) ion and arsenic (III) ion. Generally these ions are also known according to their electron configuration as s2 ions.
The co-sensitizer can also be selected from the group of the cerium (III) ion, praseodymium (III) ion, neodymium (III) ion, samarium (III) ion, europium (III) ion, gadolinium (III) ion, terbium (III) ion, dysprosium (III) ion, holmium (III) ion, erbium (III) ion, thulium (III) ion, ytterbium (III) ion and lutetium (III) ion. Generally these ions are also known according to their electron configuration as 4fn ions.
The sensitizer and where applicable the co-sensitizer reinforces the sensitivity of the down conversion luminophore for VUV radiation and makes it less wavelength-dependent. It has a high self-absorption in the required VUV range of 100 to 200 nm which essentially lies above the self-absorption of the non-sensitized down conversion luminophore at 183, 195 and 202 nm. The transmission of excitation energy to the activator pair carries losses as lattice interference causes the excitation states passing through the lattice to emit energy to the lattice in the form of heat oscillations. The reduced absorbed excitation energy is then passed to the activator and triggers the down conversion mechanism. The down conversion luminophore luminesces more intensely as it has been xe2x80x9csensitizedxe2x80x9d by the sensitizer and where applicable the co-sensitizer to luminescence capacity under VUV radiation.
The down conversion luminophore can also contain a co-activator. The co-activator is selected from the group of the trivalent ions of terbium, ytterbium, dysprosium, europium and samarium and the bivalent ions of manganese. The pair of activators of a first lanthanoid ion and a second lanthanoid ion and the co-activator ion co-operate in the sequential emission of the photons with which the luminophore generates more than one visible photon from a VUV photon.
The excitation mechanism can take place by the 8S-6G excitation of the gadolinium (III) ion which follows a cross relaxation transition between the Gd (III) ion and the holmium (III) ion or europium (III) ion. Due to the cross relaxation transition the gadolinium (III) ion changes from the 6G-state to the 6P-state, due to the released energy the holmium (III) ion changes from the 5I8-state to the 5F5-state or the europium (III) ion changes from the 7F0-state to the 5D0-state. The holmium (III) ion or the europium (III) ion then emits a visible photon, the energy of which corresponds to the transition from 5F5 to 5I8 or 5D0 to 7F1.
After an energy transfer from the 6P state of the gadolinium (III) ion to the co-activator, this also emits a visible photon.
The host lattice of the down conversion luminophore can consist of inorganic material such as fluorides, oxides, halogenides, aluminates, gallates, phosphates, borates or silicates which is doped with a few percent of both activators. The activators can be arranged on lattice places or on interstitial lattice places of the host lattice.
As a host lattice are preferred fluorides e.g. fluorides of composition M1F with M1=Li, Na, K, Rb, Cs or fluorides of composition M2F2 with M2=Mg, Ca, Sr, Ba or fluorides of composition M3F3 with M3=B, Al, In, Ga, Sc, Y, La and lanthanoids. Particularly preferred is GdF3 in which the first lanthanoid activator ion Gd3+ is part of the host lattice.
Furthermore as host lattices are preferred ternary gadolinium-containing fluorides of the composition M1GdF4, M12GdF5, M13GdF6, M1Gd2F7, M1Gd3F10, M15Gd9F32, with M1=Li, Na, K, Rb, Cs or M2GdF5, M22GdF7, M23GdF9, M2Gd2F8, M2Gd3F11, M2Gd4F14, M213Gd6F43 with M2=Mg, Ca, Sr, Ba, Mn, Zn in which gadolinium is also part of the host lattice.
Also preferred as host lattices are fluorides of the composition M1M3F4, M12M3F5, M13M3F6, M1M32F7, M1M33F10, M15M39F32 with M1=Li, Na, K, Rb, Cs and with M3=B, Al, In, Ga, Sc, Y, La, and the lanthanoids; M2M3F5, M22M3F7, M23M3F9, M2M32F8, M2M33F11, M2M34F14, M213M36F43 with M2=Mg, Ca, Sr, Ba, Mn, Zn and M3=B, Al, In, Ga, Sc, Y, La, and the lanthanoids; M3M4F7, M32M4F10, M33M4F13, M3M42F11, M3M43F15, M3M44F19 with M3=B, Al, In, Ga, Sc, Y, La, and the lanthanoids, and M4=Ti, Zr, Si, Ge, Sn, Pb.
Particularly preferred as host lattices are fluorides of which the host lattice is based on the calcium fluoride crystal lattice type. In these lattices the cations have an 8-fold co-ordination. Also particularly preferred are fluorides with a lattice derived from the YF3 crystal lattice type in which the cations have a 9-fold co-ordination. Due to the high co-ordination figures and the non-polar ligands, these host lattices are characterized by a low ligand field for cations which are part of the host lattice.
The luminophores doped with the activator pair contain preferably 10 to 99.8 mol % of the first lanthanoid ion and 0.01 to 30 mol %, particularly preferably 1.0 mol % of the second lanthanoid ion.
The down conversion luminophore can easily be doped with the trivalent co-activators terbium, ytterbium, dysprosium, europium, samarium or manganese if, in the production of the luminophores, to the starting compounds is added a fluoride selected from the group TbF3, YbF3, DyF3, EuF3, SmFe or MnF2.
The absorption co-efficient of the down conversion luminophores sensitized according to the invention is particularly large for the wavelengths in the range of xenon radiation, and the quantum efficiency levels are high. The host lattice is not a factor in the luminescence process but influences the precise position of the energy level of the activator ions and consequently the wavelengths of absorption and emission. The emission bands lie in the range from long ultraviolet to yellow-orange, but mainly in the red and green range of the electromagnetic spectrum. The extinction temperature of these luminophores is above 100xc2x0 C.
The grain size of the luminophore particles is not critical. Normally the luminophores are used as fine grain powders with a grain-size distribution between 1 and 20 xcexcm.
As a production process for luminophore layers on a wall of the discharge vessel both dry coating processes e.g. electrostatic deposition or electrostatic-supported sputtering, or wet coating processes e.g. dip coating or spraying, can be considered.
For wet coating processes the luminophore preparation must be dispersed in water, an organic solvent where applicable together with a dispersion agent, a tenside and an anti-foaming agent or a binding agent preparation. Suitable binding agent preparations for a gas discharge lamp according to the invention are organic or inorganic binding agents which tolerate an operating temperature of 250xc2x0 C. without destruction, embrittlement or discoloration.
For example the luminophore preparation can be applied to a wall of the discharge vessel by means of a flow coating process. The coating suspensions for the flow coating process contain water or an organic compound such as butylacetate as a solvent. The suspension is stabilized and its rheological properties influenced by the addition of additives such as stabilizers, liquifiers, cellulose derivatives. The luminophore suspension is applied to the vessel walls as a thin layer, dried and burned in at 600xc2x0 C.
It can also be preferred that the luminophore preparation for the luminophore layer is deposited electrostatically on the inside of the discharge vessel.
For a gas discharge lamp which is to emit white light, preferred substances are a blue-emitting luminophore from the group BaMgAl10O17:Eu2+ and Sr5(PO4)3Cl:Eu2+ combined with a red-emitting luminophore from the group ZnGdF5:Eu; Li(Gd,In)F4:Eu and (Y,Gd)BO3:Eu and with a green-emitting luminophore from the group Li(Gd,Ga)F4:Er,Tb; (Ba,Zn)PrF5:Mn and LaPO4:Ce,Tb or with a green-red-emitting luminophore (Ba,Zn)Gd2F8:Ho,Pr.
The luminophore layer usually has a layer thickness of 5 to 100 xcexcm.
The vessel is then evacuated to remove all gaseous contaminants in particular oxygen. The vessel is then filled with xenon and sealed.